Carbon monoxide is produced in a variety of incomplete oxidation processes. It appears in refinery off gas, methanol plant purge gas, blast furnace gas, water gas, coke oven gas and the gaseous effluent of steam reforming of methane. It would be highly desirable to isolate and use this carbon monoxide as a feedstock for other processes, for example, in making acetic acid. Methods for separating carbon monoxide from gas mixtures have been developed, including cryogenic distillation methods. These procedures are expensive. Therefore, there is a need for economical chemical processes for removing carbon monoxide from feed streams and recovering relatively pure carbon monoxide at the end of the separation process. Chemical separation processes are accordingly based on reversible binding of carbon monoxide with an absorbent, which will release carbon monoxide under appropriate conditions.
The separation of olefins from other hydrocarbons, including saturated hydrocarbons and aromatic hydrocarbons, is also of commercial interest. Although this can be accomplished by distillation, there is considerable interest in chemical processes, depending on selective complexation of one of a mixture of unsaturated hydrocarbons with an absorbent, which will release the hydrocarbon of interest under selected conditions.
The use of various metallic complexes has been investigated for the separation of both carbon monoxide and olefins from feed streams.
Doyle (U.S. Pat. No. 4,385,005) has proposed the use of a mixture of copper(I) or silver(I) oxide and a perfluorinated acetylacetonate to remove unsaturated hydrocarbons from feedstreams.
Carbon monoxide and alkene derivatives of copper(I) and silver(I) betadiketonates have been reported by Doyle et al., Organometallics, vol. 4 (1985), pages 830-835. These complexes are of varying stability with respect to air oxidation and disproportionation, but are insensitive to moisture.
Doyle has proposed in U.S. Pat. No. 4,279,874, using Cu(I) halogenated acetylacetonate complexes for the separation of carbon monoxide from a gas stream.
The use of Cu(I) complexes of fluorinated acetylacetone in an organic solvent for the removal of unsaturated hydrocarbons from feedstreams has been proposed by Doyle et al. in U.S. Pat. Nos. 4,434,317 and 4,508,694. The use of a stabilized cuprous fluorinated acetonylacetonate is proposed by Doyle et al. in U.S. Pat. No. 4,471,152.
Long et al. (U.S. Pat. No. 3,592,865) have recited using cuprous aluminum halide complexes to remove complexible ligands from feedstreams.
Walker, "Making and using CO," Chemtech (May, 1975), pages 308-311, has described the Cosorb purification process for separating carbon monoxide from gaseous mixtures, including streams rich in nitrogen. The process relies on stabilization of the active component, cuprous tetrachloroaluminate, in an aromatic solvent.
Dunlop et al., in U.S Pat. No. 3,401,112, have recited separating hydrocarbons of various kinds of unsaturation using cuprous salts of oxyacids.
References suggesting the state of the art of metal complexes, using organic or inorganic copper(I) or silver(I) compounds, include:
M. Bertholet, "Observations Relatives a L'action des Sels Cuivreux sur les Carbures D'hydrogene et sur L'oxyde de carbon," Ann. de Chim. et de Phys., 7th series, vol. XXIII (May, 1901), pages 32-39
M. I. Bruce, "Carbonyl Chemistry of the Group IB Metals," J. Organometal. Chem., vol. 44 (1972), pages 209-228
E. R. Gilliland et al., "Reactions of Olefins with Solid Cuprous Halides," J. Am. Chem. Soc., vol. 61 (1939), pages 1960-1962; ibid., vol. 63 (1941), pages 2088-2090
R. J. Hurtado et al., "Copper(I) Nitrile Complexes, Part III. Reversible Olefin Complex Formation with Acetonitrilecopper(I) Trifluoromethanesulfonate," Transition Met. Chem., vol. 2 (1977), pages 91-94
F. R. Hartley et al., "Influence of Solvent on the Stability of Silver(I)-Olefin Complexes," J. Chem. Soc. Dalton (1977), pages 469-477
J. Liebig, "Ueber die Constitution des Aethers und seiner Verbindungen," Ann. der Pharmacie, vol. IX (1834), pages 1--39; "Ueber die Aethertheorie, in besonderer Rucksicht suf die vorhergehende Abhandlung Zeise's", ibid., vol. 23 (1837), pages 12-42
M. A. Lur'e et al., "Separation of 1,3-Butadiene from a Mixture of Other Hydrocarbons Using Cuprous Chloride," Sinet. Kauchuk, vol. 3, no. 6 (1934), pages 19-29
S. Winstein et al., "The Coordination of Silver Ion with Unsaturated Compounds," J. Am. Chem. Soc., vol. 60 (1938), pages 836-847. Kamitori et al., Synthesis, April, 1986, pages 340-342, have recited the preparation of 3-allyl-1,1,1-trifluoroacetylacetone and related compounds, which are useful as chelating agents.